Anthraquinone bodies and process of preparing the same



Patented Dec. 22, 1931 UNITED STATES PATENT OFFICE WILLIAM I1. RINTELMAN, OF MILWAUKEE, WISCONSIN, ASSIGNOR, BY MESNE ASSIGN- MENTS, T E. I. DU PONT DEIVEMOURS & COMPANY, A CORPORATION OF DELA- WARE ANTHRAQUIN'ONE BODIES AND PROCESS OF PREPARING THE SAME No Drawing. Application filed July 2,

This invention relates to N substituted 2.6 diamino-1.5-dichloro anthraquinones and to a process of making the same. 7

It is an object of this invention to provide a methodfor preparing the N substituted 2.6-

10 studs.

Otherand further important objects of this invention will become apparent from the following description and appended claims.

In the German Patent No. 199,758 there is described a process for the chlorination of ,acetylamino anthraquinones in which it is stated that beta-amino anthraquinone is chlorinated to 1-chloro-2-amino-anthraquinone and that only one atom of chlorine enters the molecule. It is further. stated in connection with the chlorination of acidyl amino an- ,thraquinones that, according to the process described in the patent, only one atom of chlorine enters the molecule for each of the acidyl amino groups present.

I have now found that the chlorination of acidyl amino anthraquinones may be run in such a manner that more thanone atom of chlorine enters the molecule for each amino group, depending upon the excess of chlorinating agentemployed. In order to effect a chlorination of diacetylated 2.6-diamino-anthraquinone, for instance, to obtain 2.6-di- (acetyl amino) 1.5-dichloro-anthraquinone in an economical manner in accordance with my invention, it has been found advisable to use a limited quantity of chlorine, since an excess tends to introduce more than two atoms of chlorine.

I have further found that in the chlorination of N substituted diamino anthraquinones, although the chlorination will take place without an added catalyzer, the addition of small amounts of iodine appears to p I um carbonate and the like. In the place of give better results.

The extent to which the chlorination has taken place is determined by taking a test' 1928. Serial N0. 290,046.

sufficient chlorine has been introduced to correspond to the dichloro derivative.

In general, such acidyls may be employed.

which do not chlorinate appreciably in the acidylradical such as acetyl (COCH urethyl (COOC H oxalyl o oooH and the like. My invention is intended to include other nitrogen substituent-s such as toluene sulfonyl phthaloyl and the like, benzylidene In Working at higher temperatures complications are introduced, possibly due to hydrochloric acid being generated. This can'be overcome to some extent by the use of neutralizing agents, such as sodium acetate, sodichlorine as such for the chlorination, other chlorlnating agents, as for example, sodium "hypochlorite and hydrochloric acid may be used, but they are not to be preferred. During thestep of chlorinating in aceticacid on an isolated portion checked up for chlowithchlorine, an intermediate product, possibly a nitrogen chloride, may be isolated as such and transformed as such after isolation.

The I l-substituted 2.o-diamino-l.5dichloro anthraquinones are in general similar to 2.6- di- (acetyl amino) -1.5- di'chl'oro anthraquinone, which has the following characteris-- tics: It is a yellowsol1d,spar1ngly soluble in warm acetic acid, less so in cold acetic acid and practically insoluble in water. It is soluble in concentrated sulfuric acid, lmparting thereto a greenish coloration (probably dueto traces of the intermediate nitrogen-chloride compound above referred to) but'insoluble in diluted acids and alkalies.

drolysis or" similar bodies to 2.6-diamino-1.5- dichloro .anthraquinone. The 2.6-di-(acetyl amino) -1.5-dichloro anthraquinone does not melt below 300 C.

Without limiting my invention to any particular procedure, th following example in which parts by weight are given, will serve to illustrate my method in its preterrec form.

Example Add 10 parts of 2.6-diamino anthraquinone chlorine content corresponding to 18 to 19% chlorine. The mass is then agitated at 35 to is practically completed. From time to time samples are taken and the chlorine analysis rine content. The finished test should show 18 to 19% chlorine content, otherwise more Y chlorine should be passed'in. Upon completion of the chlorlnation, the mass is filtered A at 25to 30 C. and washed with about parts of glacial acetic. acid and with some hot water to remove the inorganic residues. It is then Other Zddi (acidyl amino) anthraquinones may be chlorinated in a similar man nor to produce 2.6-di-(acidyl amino) -1.5-. dichloro anthra'quinones whichmay be used; for similar purposes as the diacetylbody described. V

I am aware that numerous details of the process may be'varied through a wide range without departing from the principles of this -1nvent1on,-and I, therefore, do not purpose it can be hydrolyzed by methods-applicable to the-hyof the following formula: 40 0. till the chlorinationto the Lei-position 1 scril limiting the patent granted hereon otherwise than necessitated by the prior art.

I claim as my invention:

1. The process of preparing an N substituted 2.tS-diamino-l.o-dichloro anthraquinone, which comprises chlorinating 2.6-di- (-acidyl amino) anthraquinone until chlorination to trie- Lo-position is practically complete.

The process of preparing 2.6-di-(acetyl amino)-1.5-dichloro anthraquinone, which comprises chlorinating 2.6-di- (acetyl amino) anthraquinone until chlorination to the 1.5- position is practically complete. c 1

3. The process of preparing 2.6-di-(acetyl amino) 1.5-dichloro anthraqui-none, which comprises chlorinating 2.6-di-(acetyl amino) anthraquinone at a temperature of about 35 to4l0 O. in glacial acetic acid in the presence of sodium acetate and iodine until chlorina tion to the 1.5 position is practically complete.

The process or preparing 2.6-di-(acetyl amino)-l.5-dichloro anthraquinone, which comprises acetylating 2.6-diamino anthraqui none in glacial acetic acid and acetic acid anhydride and without-isolation of the intermediate product passing chlorine into the solution in the presence of sodium acetate and iodine at a temperature of about 35 to 40 C. until'chlorination to the l.5jposition is practically complete. 7

5. [is new articles of manufacture, 2.6-di- (acidyl' 1 amino)-1.5-dichloro nones. 1 4 7 6. As new articles of manufacture, 2.6-di- ('acetyl' amino)'-1-.5-dichloro anthraquinone c1 CO "In testimonywhereot' I have hereunto subany name at Carrollville, Milwaukee County, tvlsconsln. v

WILLIAM L. RINTELMAN. 

